Liquid pepper composition and process for producing the same



patented June 8,

2,680,690 ICE LIQUID PEPPER COMPOSITION AND PROC- ESS FOR PRODUCING THESAME Frederick R. Schumm, Jersey City, N. J., and Claude Johnstone,Hicksville, N. Y., assignors to Dodge & Olcott, Inc., New York, N. Y., acorporation of Delaware No Drawing. Application May 2, 1952, Serial No.285,798

9 Claims.

This invention relates to solubilized pepper compositions derived fromthe oleoresin of members of the Piperaceae family, and provides liquidpiperin compositions especially useful for the seasoning of foods andalso an improved method by which these compositions may, with advantage,be prepared.

Oleoresins derived from the plant, Piper nigrum L., i. e., black pepper,and from other members of the Piperaceae family, contain a considerableamount of piperin, an ingredient responsible for much of the bite andpungency characteristics of pepper and of the oleoresins made fromplants of this family. However, commercial oleoresins of this type arenon-homogeneous products, consisting primarily of essential and fixedoils as a liquid phase, and a solid phase consisting essentially ofpiperin. The relative insolubility of the piperin results in a slowtasteperception of its pepper-like qualities.

The primary commercial use of the oleoresins of pepper is in themanufacture of food seasoning compositions. For this purpose, theinsolubility of the piperin has been found objectionable and hasmitigated against their use as such and the ready, economical productiontherefrom of other uniform seasoning compositions.

In our copending application Serial No. 193,- 536, filed November 1,1950, now Patent No. 2,626,218 issued January 20, 1953, We havedescribed and claimed a homogeneous liquid pepper composition, and aprocess for producing such composition which comprises mixing with anoleoresin of pepper a substantially anhydrous, normally liquid organicacid, which is miscible with the essential oils of the oleoresin.

The process of said copending application has been used with markedsuccess. Its use is, however, subject to the disadvantage that many ofthe organic acids which are miscible with the essential oils of theoleoresins, and particularly those Which have gained acceptance asingredients of food for human consumption, possess characteristic tastesor odors and tend to alter somewhat the natural pepper taste, or aroma.This is particularly true of acetic acid and butyric acid. On the otherhand, levulinic acid, which is entirely free from these objections, andalso pyruvic acid, are not readily obtainable in the present day market.

We have now discovered that anhydrous lactic acid, which has long beenaccepted as a constituent of food for human consumption, may be used,with advantage, in producing solubilized pepper compositions from theoleoresins of pepper.

Like levulinic acid, anhydrous lactic acid, is substantially free fromobjectionable taste and odor, and also has the properties ofsolubilizing the solid phase of commercial oleoresins, consistingessentially of piperin. Unlike levulinic acid, lactic acid is readilyavailable but is not soluble in, or miscible with, the essential oils ofthe oleoresins to any substantial extent and, therefore, does not form astable homogeneous liquid phase when mixed with the oleoresins.

We have found, however, that where substantially anhydrous lactic acidis mixed with an oleoresin of pepper, not only is the piperinsolubilized, but also there is produced a thick, viscous mixture of thesolubilized piperin and the oil constituents of the oleoresin of thenature of an emulsion. On warming, this mixture becomes more fluid andseparates into two liquid layers. But, at normal temperatures, themixture is very slow to separate, and when well mixed, separates soslowly at normal temperatures as to permit the withdrawal of a uniformcomposition from the container over extended periods of time. At low ormoderate temperatures, the mixture possesses many of the advantages ofthe homogeneous liquid pepper composition prepared by mixing levulinicacid with the oleoresin.

Predicated upon this discovery, our present invention comprises themixing of anhydrous lactic acid with an oleoresin of pepper, forinstance, a commercial oleoresin, or an equivalent composition, such asextracted from pepper corns, in accordance with conventional procedure.The mixing of these materials is advantageously carried out at roomtemperature.

The lactic acid used in accordance with our present invention, must besubstantially anhydrous and is, with advantage, prepared from U. S. P.grade lactic acid, which consists essentially of a mixture of lacticacid and lactic anhydride, the former constituting to of the mixture.This anhydrous lactic acid may be prepared, for instance, by heating 85%U. S. P. lactic acid, at atmospheric pressure, until 15% by weight ofwater has been distilled 01f, or until the temperature of the boilingliquid reaches C. Some lactic anhydride is usually formed during thedehydration of lactic acid and such mixtures are included by the termanhydrous lactic acid, as used herein.

The proportion of the lactic acid to oleoresin may be varied within therange of about one part to about three parts of the anhydrous lacticacid, for each three parts of oleoresin by weight. The use of about onepart of the acid for each two parts of the oleoresin has been found togive generally satisfactory results. We have found,

however, that where less than about one part of 7 acid for each threeparts of oleoresin is used, the piperin is likely to be precipitatedfrom solution if subjected to low temperatures, such as frequentlyencountered in winter weather. We have further found that, while inexcess of one part of the acid per part of the oleoresin may be usedresins of pepper, as previously indicated, may be prepared byconventional procedure. Such procedure usually consists in theextraction of dry, ground pepper corns by a volatile solvent such asether, alcohol, acetone, methylene chloride, chloroform, hexane,heptane, or the like. Following the extraction, the solvent is usuallyremoved by distillation at moderate temperatures, the resultant residueconstituting the oleoresin of the pepper; This product, as previouslystated, is composed of a solid phase, constituting the piperin andnatural resins, and a liquid phase consisting of fixed and essentialoils. Upon standing, the solid phase will form a hard, crystalline masswhich frequently must be heated to its softening point before readyremoval from its container is possible. Such heating must be carefullycontrolled as any overheating deleteriously afiects the odor of thepepper composition. By our present invention, the normally solid piperinis solubilized so that such previously experienced difiiculties areavoided.

The invention will be more particularly described and. illustrated bythe following specific example of its application to black peppercompositions. It will be understood, however, that the invention issimilarly applicable to other members of the Piperaceae family.

Four thousand pounds of black pepper corns are dried, ground to meshsize and extracted with acetone in the conventional type of continuousextraction apparatus until the extraction of the oleoresin is complete.The resultant extract is then distilled at atmospheric pressure toremove the major portion of the solvent, the distillation beingcontinued until the residual liquid closed. and the distillationcontinued with agitae tion, at an absolute pressure of about 1 pound persquare inch, until the last of the solvent is distilled off. In thisdistillation operation, the temperature of the liquid is not permittedto exceed 150 F.

It will: be understood that, in place of acetone, other volatilesolvents for the oleoresins, such as previously mentioned herein, may beused and the temperature used in distilling off the solvents will bedictated largely by the boiling point of theparticular solvent selected.Temperatures at which substantial decomposition of the oleoresin iseffected should, of course, be avoided.

Upon cooling and agitating, a thick viscous emulsion, composed ofsolubilized piperin and the oil constituent of the oleoresin, of thetype previously described herein, is produced.

In the foregoing example, the anhydrous lactic acid was added to theoleoresin while the latter still contained a small amount of theextractive solvent. We have found that the presence of a small amount ofthe solvent is advantageous as it iacilitates the mixing of the lacticacid with the oleoresin. It is understood, however, that the presence ofthe solvent is not essential to our presout process, and when thesolvent is not present, the subsequent heating at reduced pressure will,of course, be unnecessary. Where desired, ordinary oleoresins ofcommerce, free from extractive solvents, may be used as the startingmaterial.

Where the subsequent distillation, at reduced pressure, is employed toremove residual extractive solvent, excessive temperatures should beavoided so as to preserve the natural taste and aroma of the pepper.

We claim:

1. The process for producing liquid pepper compositions which comprisesadding to, and mixing with, an oleoresin of pepper, anhydrous lacticacid in an amount effective to solubilize the piperin.

2. The process of producing liquid pepper compositions which comprisesadding to, and mixing with, an oleoresin of pepper, in the presence of arelatively small proportion of an organic solvent, substantiallyanhydrous lactic acid in an amount cfiective to solubilize the piperinand distilling ofi the organic solvent at reduced pressure.

3. The process for producing liquid pepper compositions which comprisesadding to, and mixing with, an oleoresinof pepper, anhydrous lacticacid, the proportion of the lactic acid to the oleoresin used being notless than about 1:3, by weight.

4. The process for producing liquid pepper composition which com-prisesadding to, and mixing with, an oleoresin of pepper, anhydrous lacticacid, the proportion of lac tic acid used being within the range of 1 to3 parts of the acid for each 3 parts of the oleoresin, by weight.

5. Process for producing liquid pepper compositions which comprisesadding to, and mixing with, an oleoresin of pepper, anhydrous lacticacid, the proportion of lactic acid to the oleoresin usedbeing about1:2, by weight.

6. A pepper composition. comprising piperin solubilizedin substantiallyanhydrous lactic acid.

'7. A thick, viscous liquid pepper composition consisting essentially ofsolubilized piperin, the oils normally present inoleoresins of pepperand substantially anhydrous lactic acid.

8. A thick, viscous liquidv pepper composition consisting essentially ofsolubilized piperin, the oils normally present in olcoresinsof pepperand substantially anhydrous lactic acid, the proportion of lactic acidbeing within the rangeof 1 tot) partsof the acid to each. 3- parts ofthe other two named constituents, by weight.

9. A thick, viscous liquid pepper composition consisting essentially ofsolubiliaed piperin, the oils normally. present in oleoresins ofpepperand substantially anhydrous lactic acid, the proper tion of lacticacidbeing about half the summation. of the weight of the other twonamedconstituents.

References Citedin thefile,- of this patent; UNITED s'rATEs PATENTSNumber Name Date I 1,602,183 Thomssen, Qct. 5, 1926' 2,079,415 LevinsonMay. 4,1937,

1. THE PROCESS FOR PRODUCING LIQUID PEPPER COMPOSITIONS WHICH COMPRISESADDING TO , AND MIXING WITH, AN OLEORESIN OF PEPPER, ANHYDROUS LACTICACID IN AN AMOUNT EFFECTIVE TO SOLUBILIZE THE PIPERIN.